- One-pot sandmeyer trifluoromethylation and trifluoromethylthiolation
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Practical one-pot procedures were developed for both Sandmeyer-type trifluoromethylations and trifluoromethylthiolations. Starting from broadly available (hetero)aromatic amines, various benzotrifluorides were synthesized in high yields via in situ diazotization and copper-mediated trifluoromethylation using the inexpensive Ruppert-Prakash trifluoromethylating reagent. In the presence of sodium thiocyanate as a sulfur source, aryl trifluoromethyl thioethers are exclusively formed.
- Bayarmagnai, Bilguun,Matheis, Christian,Risto, Eugen,Goossen, Lukas J.
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Read Online
- Methyl 3-Oxa-ω-fluorosulfonylperfluoropentanoate: a Versatile Trifluoromethylating Agent for Organic Halides
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Methyl 3-oxa-ω-fluorosulfonylperfluoropentanoate FSO2CF2CF2OCF2CO2Me 1, prepared through the reaction of readily available ICF2CF2OCF2CF2SO2F and SO3 followed by MeOH, is a very convenient trifluoromethylating agent; in the presence of copper(I) iodide, 1 not only reacts with vinyl, benzyl allyl, phenyl iodides and bromides, but also with aryl chlorides to give the corresponding trifluoromethyl compounds in moderate to high yield; a probable reaction mechanism is proposed.
- Chen, Qing-Yun,Duan, Jian-Xing
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Read Online
- Synthesis of 2-methyl-1,5-dinitro-3- and 2-methyl-1,3-dinitro-5-(trifluoromethyl)benzenes and their transformation into 6-nitro-4-(trifluoromethyl)- and 4-nitro-6-(trifluoromethyl)-1H-indoles
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A facile two-step synthesis of 2-methyl-1,5-dinitro-3- and 2-methyl-1,3-dinitro-5-(trifluoromethyl)benzenes is described. The first step is the nitration of otho- and para-methylbenzoic acids to furnish the corresponding dinitroacids. The dinitroacids then react with sulfur tetrafluoride to provide the corresponding trifluoromethylated products. The latter are easily transformed into 6-nitro-4-(trifluoromethyl)- and 4-nitro-6-(trifluoromethyl)-1H-indoles by applying the Batcho-Leimgruber synthetic protocol.
- Petruk, Oksana M.,Kyriukha, Yevhenii A.,Bezdudny, Andriy V.,Rozhkov, Vladimir V.
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Read Online
- Flash Thermolysis of Aryl Trifluoroacetates: A New Approach to Trifluoromethylated Aromatic Compounds
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Flash thermolysis of aryl trifluoroacetates yield trifluoromethyl aromatic compounds along with trifluoromethoxy compounds.
- Kobayashi, Y.,Nakazato, A.,Kumadaki, I.,Filler, R.
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Read Online
- Phosphovanadomolybdic acid catalyzed direct C-H trifluoromethylation of (hetero)arenes using NaSO2CF3 as the CF3 source and O2 as the terminal oxidant
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A direct C-H trifluoromethylation of (hetero)arenes using NaSO2CF3 (Langlois' reagent) as the CF3 source and O2 as the terminal oxidant has been developed. In the presence of catalytic amounts of phosphovanadomolybdic acids, such as H6PV3Mo9O40, various kinds of substituted benzenes and heteroaromatic compounds could be converted into the corresponding trifluoromethylated products.
- Li, Chifeng,Suzuki, Kosuke,Yamaguchi, Kazuya,Mizuno, Noritaka
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Read Online
- Use of methyllithium in metal/halogen exchange; a mild and efficient method for the synthesis of ortho substituted toluenes
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Methyllithium, in the presence of excess methyl iodide, can be used to convert suitably substituted aromatic bromides to the corresponding toluenes under mild conditions and in high yield.
- Andrews,Kitteringham,Voyle
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Read Online
- Generation of trifluoromethylcopper from chlorodifluoroacetate
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In the presence of fluoride ion, methyl chlorodifluoroacetate undergoes halide ion-promoted decarboxylation to give trifluoromethide which can be trapped with cuprous iodide.The resulting trifluoromethyl copper reagent has been observed spectroscopically and can be trapped with aryl iodides to give the corresponding trifluoromethylaromatic compound.
- MacNeil, James G.,Burton, Donald J.
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Read Online
- Ligand-free trifluoromethylation of iodoarenes by use of 2-Aryl-2-trifluoromethylbenzimidazoline as new trifluoromethylating reagent
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N-Methyl 2-aryl-2-trifluoromethylbenzimidazolines were synthesized and utilized in the trifluoromethylation reaction of iodoarenes in the presence of copper(I) salt and base. Iodoarenes bearing electron-donating and electron-withdrawing groups were tolerant to this reaction in the absence of a ligand and gave trifluorotoluene derivatives in good to high yields.
- Miyagawa, Masamichi,Ishikawa, Taisuke,Shinkai, Kota,Akiyama, Takahiko
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Read Online
- Comparative profiling of well-defined copper reagents and precursors for the trifluoromethylation of aryl iodides
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A number of copper reagents were compared for their effectiveness in trifluoromethylating 4-iodobiphenyl, 4-iodotoluene, and 2-iodotoluene. Yields over time were plotted in order to refine our understanding of each reagent performance, identify any bottlenecks, and provide more insight into the rates of the reactions. Interestingly, differences in reactivity were observed when a welldefined [LCuCF3] complex was employed directly or generated in situ from precursors by published reports. Relative reactivities were also found to highly dependent on the nature of the iodoarenes.
- Kaplan, Peter T.,Lloyd, Jessica A.,Chin, Mason T.,Vicic, David A.
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Read Online
- Cross-Coupling through Ag(I)/Ag(III) Redox Manifold
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In ample variety of transformations, the presence of silver as an additive or co-catalyst is believed to be innocuous for the efficiency of the operating metal catalyst. Even though Ag additives are required often as coupling partners, oxidants or halide scavengers, its role as a catalytically competent species is widely neglected in cross-coupling reactions. Most likely, this is due to the erroneously assumed incapacity of Ag to undergo 2e? redox steps. Definite proof is herein provided for the required elementary steps to accomplish the oxidative trifluoromethylation of arenes through AgI/AgIII redox catalysis (i. e. CEL coupling), namely: i) easy AgI/AgIII 2e? oxidation mediated by air; ii) bpy/phen ligation to AgIII; iii) boron-to-AgIII aryl transfer; and iv) ulterior reductive elimination of benzotrifluorides from an [aryl-AgIII-CF3] fragment. More precisely, an ultimate entry and full characterization of organosilver(III) compounds [K]+[AgIII(CF3)4]? (K-1), [(bpy)AgIII(CF3)3] (2) and [(phen)AgIII(CF3)3] (3), is described. The utility of 3 in cross-coupling has been showcased unambiguously, and a large variety of arylboron compounds was trifluoromethylated via [AgIII(aryl)(CF3)3]? intermediates. This work breaks with old stereotypes and misconceptions regarding the inability of Ag to undergo cross-coupling by itself.
- Demonti, Luca,Mézailles, Nicolas,Nebra, Noel,Saffon-Merceron, Nathalie
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supporting information
p. 15396 - 15405
(2021/10/12)
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- Nickel/Photoredox-Catalyzed Methylation of (Hetero)aryl Chlorides Using Trimethyl Orthoformate as a Methyl Radical Source
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Methylation of organohalides represents a valuable transformation, but typically requires harsh reaction conditions or reagents. We report a radical approach for the methylation of (hetero)aryl chlorides using nickel/photoredox catalysis wherein trimethyl orthoformate, a common laboratory solvent, serves as a methyl source. This method permits methylation of (hetero)aryl chlorides and acyl chlorides at an early and late stage with broad functional group compatibility. Mechanistic investigations indicate that trimethyl orthoformate serves as a source of methyl radical via β-scission from a tertiary radical generated upon chlorine-mediated hydrogen atom transfer.
- Kariofillis, Stavros K.,Shields, Benjamin J.,Tekle-Smith, Makeda A.,Zacuto, Michael J.,Doyle, Abigail G.
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supporting information
p. 7683 - 7689
(2020/04/22)
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- Cathodic C-H Trifluoromethylation of Arenes and Heteroarenes Enabled by an in Situ-Generated Triflyltriethylammonium Complex
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While several trifluoromethylation reactions involving the electrochemical generation of CF3 radicals via anodic oxidation have been reported, the alternative cathodic, reductive radical generation has remained elusive. Herein, the first cathodic trifluoromethylation of arenes and heteroarenes is reported. The method is based on the electrochemical reduction of an unstable triflyltriethylammonium complex generated in situ from inexpensive triflyl chloride and triethylamine, which produces CF3 radicals that are trapped by the arenes on the cathode surface.
- Cantillo, David,Jud, Wolfgang,Kappe, C. Oliver,Maljuric, Snjezana
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supporting information
(2019/10/08)
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- Stoichiometric and Catalytic Aryl-Perfluoroalkyl Coupling at Tri-tert-butylphosphine Palladium(II) Complexes
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This Communication describes studies of Ph-RF (RF = CF3 or CF2CF3) coupling at Pd complexes of general structure (PtBu3)PdII(Ph)(RF). The CF3 analogue participates in fast Ph-CF3 coupling (II complex. Furthermore, they show that this undesired pathway can be circumvented by changing from a CF3 to a CF2CF3 ligand. Ultimately, the insights gained from stoichiometric studies enabled the identification of Pd(PtBu3)2 as a catalyst for the Pd-catalyzed cross-coupling of aryl bromides with TMSCF2CF3 to afford pentafluoroethylated arenes.
- Ferguson, Devin M.,Bour, James R.,Canty, Allan J.,Kampf, Jeff W.,Sanford, Melanie S.
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supporting information
p. 11662 - 11665
(2017/09/07)
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- The first nucleophilic C-H perfluoroalkylation of aromatic compounds via (arene)tricarbonylchromium complexes
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The first nucleophilic perfluoroalkylation of arenes is based on the arene π-system activation via (η6-arene)tricarbonylchromium complexes. Perfluoroalkyl anions generated from Me3SiRF and a fluoride ion source [Me4N]F exclusively attack the arene ligand under mild conditions. The formed negatively charged analogs of Meisenheimer adducts readily undergo a one-pot oxidation to perfluoroalkyl arenes.
- Kirij, Natalia V.,Filatov, Andrey A.,Khrapach, Gleb Yu.,Yagupolskii, Yurii L.
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supporting information
p. 2146 - 2149
(2017/02/19)
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- Trifluoroacetic acid copper (I) reagent and its application in the trifluoromethylation reaction
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The invention discloses a copper trifluoroacetate (I) reagent and application thereof in trifluoromethylate reaction. The structural formula is disclosed in the specification. The copper trifluoroacetate (I) reagent is prepared by the following steps: reacting cuprous chloride, sodium tert-butyl alcoholate and bidentate nitrogen ligand in a tetrahydrofuran solvent, adding trifluoroacetic acid to react, and finally, carrying out separation purification to obtain the copper trifluoroacetate (I) reagent. The reagent can perform trifluoromethylation reaction with halogenated aromatic hydrocarbons or halogenated heterocyclic compounds in a decarboxylation mode to form the corresponding trifluoromethylation derivates. The method has the advantages of simple preparation technique and cheap and accessible raw materials; and the obtained copper trifluoroacetate (I) reagent has favorable selectivity, can promote the trifluoromethylation reaction to proceed quickly and efficiently, and has favorable industrial application prospects.
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Paragraph 0031; 0032
(2017/03/25)
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- Trifluoromethylation of haloarenes with a new trifluoro-methylating reagent Cu(O2CCF2SO2F)2
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A new trifluoromethylating reagent Cu(O2CCF2SO2F)2, which easily decomposes to generate active CuCF3 species in DMF at room temperature, has been conveniently prepared from inexpensive starting materials on a large scale. This new reagent can be applied to efficiently trifluoromethylate a variety of haloarenes under mild conditions, providing good-to-excellent yields of the desired products.
- Zhao, Gang,Wu, Hao,Xiao, Zhiwei,Chen, Qing-Yun,Liu, Chao
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p. 50250 - 50254
(2016/06/15)
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- Copper-catalysed synthesis of trifluoromethyl(hetero)arenes from di(hetero)aryl-λ3-iodanes
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An efficient synthesis of trifluoromethylated (hetero)arenes has been achieved through the regioselective copper-catalyzed trifluoromethylation of di(hetero)aryl-λ3-iodanes, employing readily available trifluoromethyltrimethylsilane. The reaction works well for both symmetrical and unsymmetrical di(hetero)aryl-λ3-iodanes with good regioselectivity and also tolerates diverse functional groups such as bromo, iodo, cyano, nitro, ester, ketone and enolizable ketone.
- Pandey, Vinay Kumar,Anbarasan, Pazhamalai
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p. 18525 - 18529
(2016/02/27)
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- Decarboxylative Trifluoromethylating Reagent [Cu(O2CCF3)(phen)] and Difluorocarbene Precursor [Cu(phen)2][O2CCF2Cl]
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This article describes the new economic decarboxylative trifluoromethylating reagent [Cu(phen)(O2CCF3)] (1; phen=1,10-phenanthroline) and the efficient difluorocarbene precursor [Cu(phen)2][O2CCF2Cl] (2). Treatment of copper tert-butoxide with phen and subsequent addition of trifluoroacetic acid or chlorodifluoroacetic acid afforded air-stable complexes 1 and 2, respectively, which were characterized by X-ray crystallography. The copper(I) ion in 1 is coordinated by a bidentate phen ligand, a monodentate trifluoroacetate group, and a molecule of CH3CN in a distorted tetrahedral coordination geometry. The molecular structure of 2 adopts an ionic form that consists of a [Cu(phen)2]+ cation and a chlorodifluoroacetate anion. Complex 1 reacted with a variety of aryl and heteroaryl halides to form trifluoromethyl (hetero)arenes in good yields. The corresponding Hammett plot exhibited a linear relationship and a reaction parameter (ρ)=+0.56±0.02, which indicated that the trifluoromethylation reaction proceeded via a nucleophilic reactive species. Complex 2 reacts with phenols to produce aryl difluoromethyl ethers in modest-to-excellent yields. Mechanistic investigations revealed that the difluoromethylation reaction proceeds by initial copper-mediated formation of difluorocarbene and subsequent concerted addition of difluorocarbene to the phenol to form a three-center transition state.
- Lin, Xiaoxi,Hou, Chuanqi,Li, Haohong,Weng, Zhiqiang
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supporting information
p. 2075 - 2084
(2016/02/12)
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- Introducing a new radical trifluoromethylation reagent
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Perfluoro-3-ethyl-2,4-dimethyl-3-pentyl radical (PPFR) is a persistent radical stable at room temperature, but easily decomposes at 90 °C to produce a CF3 radical which is able to react with a variety of aromatic compounds to afford the corresponding trifluoromethyl derivatives, usually as mixtures of regioisomers in good to excellent overall yields.
- Sato, Azusa,Han, Jianlin,Ono, Taizo,Wzorek, Alicja,Ace?a, José Luis,Soloshonok, Vadim A.
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supporting information
p. 5967 - 5970
(2015/03/30)
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- Catalytic cycle for palladium-catalyzed decarbonylative trifluoromethylation using trifluoroacetic esters as the CF3 source
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This paper demonstrates a catalytic cycle for Pd-catalyzed decarbonylative trifluoromethylation using trifluoroacetic esters as CF3 sources. The proposed cycle consists of four elementary steps: (1) oxidative addition of a trifluoroacetic ester to Pd0, (2) CO deinsertion from the resulting trifluoroacyl PdII complex, (3) transmetalation of a zinc aryl to PdII, and (4) aryl-CF3 bond-forming reductive elimination. The use of RuPhos as the supporting ligand enables each of these steps to proceed under mild conditions (3 sources.
- Maleckis, Ansis,Sanford, Melanie S.
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p. 2653 - 2660
(2014/06/10)
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- Copper-mediated trifluoromethylation of aryl-, heteroaryl-, and vinyltrifluoroborates with Langlois' reagent
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An effortless and realistic procedure for the copper-mediated trifluoromethylation of aryl-, heteroaryl- and vinyltrifluoroborates with CF3 radicals generated from NaSO2CF3 and tert-butyl hydroperoxide (TBHP) is presented. The developed method produces trifluoromethyl arenes and -alkenes in good to excellent yields and a wide range of electronically and structurally diverse substrates are tolerated.
- Dubbaka, Srinivas Reddy,Salla, Manohar,Bolisetti, Raghu,Nizalapur, Shashidhar
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p. 6496 - 6499
(2014/02/14)
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- DIRECT TRIFLUOROMETHYLATIONS USING TRIFLUOROMETHANE
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A direct trifluoromethylation method preferably using a trifluoromethane as a fluoro-methylating species. In particular, the present method is used for preparing a trifluoromethylated substrate by reacting a fluoromethylatable substrate with a trifiuoromethylating agent in the presence of an alkoxide or metal salt of silazane under conditions sufficient to trifluoromethylate the substrate; wherein the fluoromethylatable substrate includes chlorosilanes, carbonyl compounds such as esters, aryl halides, aldehydes, ketones, chalcones, alkyl formates, alkyl halides, aryl halides, alkyl borates, carbon dioxide or sulfur.
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Paragraph 0049
(2014/03/25)
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- Trifluoromethylation of aryl and heteroaryl halides with fluoroform-derived CuCF3: Scope, limitations, and mechanistic features
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Fluoroform-derived CuCF3 recently discovered in our group exhibits remarkably high reactivity toward aryl and heteroaryl halides, performing best in the absence of extra ligands. A broad variety of iodoarenes undergo smooth trifluoromethylation with the ligandless CuCF3 at 23-50 C to give the corresponding benzotrifluorides in nearly quantitative yield. A number of much less reactive aromatic bromides also have been trifluoromethylated, including pyridine, pyrimidine, pyrazine, and thiazole derivatives as well as aryl bromides bearing electron-withdrawing groups and/or ortho substituents. Only the most electrophilic chloroarenes can be trifluoromethylated, e.g., 2-chloronicotinic acid. Exceptionally high chemoselectivity of the reactions (no side-formation of arenes, biaryls, and C2F5 derivatives) has allowed for the isolation of a large number of trifluoromethylated products in high yield on a gram scale (up to 20 mmol). The CuCF3 reagent is destabilized by CuX coproduced in the reaction, the magnitude of the effect paralleling the Lewis acidity of CuX: CuCl > CuBr > CuI. While SNAr and SRN1 mechanisms are not operational, there is a well-pronounced ortho effect, i.e., the enhanced reactivity of ortho-substituted aryl halides 2-RC6H4X toward CuCF3. Intriguingly, this ortho-effect is observed for R = NO2, COOH, CHO, COOEt, COCH3, OCH3, and even CH3, but not for R = CN. The fluoroform-derived CuCF3 reagent and its reactions with haloarenes provide an unmatched combination of reactivity, selectivity, and low cost.
- Lishchynskyi, Anton,Novikov, Maxim A.,Martin, Eddy,Escudero-Adan, Eduardo C.,Novak, Petr,Grushin, Vladimir V.
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p. 11126 - 11146
(2013/12/04)
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- Sandmeyer trifluoromethylation of arenediazonium tetrafluoroborates
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Copper capabilities: Diazonium salts are converted into the corresponding trifluoromethyl derivatives in the presence of a trifluoromethyl-copper complex generated in situ from CuSCN and the inexpensive, easy-to-use trifluoromethylating reagent Me3Si-CF3 (see scheme). This Sandmeyer-type reaction allows the straightforward synthesis of trifluoromethylated arenes and heteroarenes from the corresponding amines. Copyright
- Danoun, Grégory,Bayarmagnai, Bilguun,Grünberg, Matthias F.,Goo?en, Lukas J.
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p. 7972 - 7975
(2013/08/23)
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- Practical method for the Cu-mediated trifluoromethylation of arylboronic acids with CF3 radicals derived from NaSO2CF3 and tert-butyl hydroperoxide (TBHP)
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A mild and practical protocol for the copper-mediated trifluoromethylation of aryl and heteroaryl boronic acids using NaSO2CF3 (Langlois' reagent) and TBHP is described. The reaction proceeds at room temperature under ambient conditions, and the products can be readily purified by extraction or column chromatography.
- Ye, Yingda,Kuenzi, Stefan A.,Sanford, Melanie S.
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supporting information
p. 4979 - 4981,3
(2012/12/12)
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- Practical method for the Cu-mediated trifluoromethylation of arylboronic acids with CF3 radicals derived from NaSO2CF3 and tert-butyl hydroperoxide (TBHP)
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A mild and practical protocol for the copper-mediated trifluoromethylation of aryl and heteroaryl boronic acids using NaSO2CF3 (Langlois' reagent) and TBHP is described. The reaction proceeds at room temperature under ambient conditions, and the products can be readily purified by extraction or column chromatography.
- Ye, Yingda,Künzi, Stefan A.,Sanford, Melanie S.
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supporting information
p. 4979 - 4981
(2013/01/15)
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- Fluoroform-derived CuCF3 for low-cost, simple, efficient, and safe trifluoromethylation of aryl boronic acids in air
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Easy does it: Aryl boronic acids undergo smooth and selective trifluoromethylation with low-cost fluoroform-derived CuCF3 in DMF in non-dried air. The reaction occurs under mild conditions (1 atm, room temperature), exhibits unprecedented funct
- Novak, Petr,Lishchynskyi, Anton,Grushin, Vladimir V.
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supporting information; experimental part
p. 7767 - 7770
(2012/08/29)
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- FLUOROALKYLATION METHODS AND REAGENTS
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A method of forming a fluorinated molecular entity includes reacting in a reaction mixture an aromatic halide, copper, a fluoroalkyl group, and a ligand. The aromatic halide includes an aromatic group and a halogen substituent bonded to the aromatic group. The ligand includes at least one group-V donor selected from phosphorus and an amine. The overall molar ratio of copper to aromatic halide in the reaction mixture is from 0.2 to 3. The method further includes forming a fluoroalkylarene including the aromatic group and the fluoroalkyl group bonded to the aromatic group. A composition, which may be used in the method, consists essentially of copper, the fluoroalkyl group, and the ligand, where the molar ratio of copper to the fluoroalkyl group is approximately 1.
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Page/Page column title page; 6; 28
(2012/03/11)
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- Silver-mediated trifluoromethylation of arenes using TMSCF3
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The silver-mediated C-H trifluoromethylation of aromatic substrates using TMSCF3 is described. The development, optimization, and scope of these transformations are reported. AgCF3 intermediates are proposed.
- Ye, Yingda,Lee, Shin Hee,Sanford, Melanie S.
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supporting information; experimental part
p. 5464 - 5467
(2011/12/05)
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- Mechanistic and computational studies of oxidatively-induced Aryl-CF 3 bond-formation at Pd: Rational design of room temperature aryl trifluoromethylation
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This article describes the rational design of first generation systems for oxidatively induced Aryl-CF3 bond-forming reductive elimination from PdII. Treatment of (dtbpy)PdII(Aryl)(CF3) (dtbpy = di-tert-butylbipyridine) with NFTPT (N-fluoro-1,3,5-trimethylpyridinium triflate) afforded the isolable PdIV intermediate (dtbpy)Pd IV(Aryl)(CF3)(F)(OTf). Thermolysis of this complex at 80 °C resulted in Aryl-CF3 bond-formation. Detailed experimental and computational mechanistic studies have been conducted to gain insights into the key reductive elimination step. Reductive elimination from this PdIV species proceeds via pre-equilibrium dissociation of TfO- followed by Aryl-CF3 coupling. DFT calculations reveal that the transition state for Aryl-CF3 bond formation involves the CF3 acting as an electrophile with the Aryl ligand serving as a nucleophilic coupling partner. These mechanistic considerations along with DFT calculations have facilitated the design of a second generation system utilizing the tmeda (N,N,N′,N′-tetramethylethylenediamine) ligand in place of dtbpy. The tmeda complexes undergo oxidative trifluoromethylation at room temperature.
- Ball, Nicholas D.,Gary, J. Brannon,Ye, Yingda,Sanford, Melanie S.
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supporting information; experimental part
p. 7577 - 7584
(2011/06/25)
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- Cooperative effect of silver in copper-catalyzed trifluoromethylation of aryl iodides using Me3SiCF3
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An effective model of cooperative effect of silver for the coppercatalyzed trifluoromethylation of activated and unactivated aryl iodides to trifluoromethylated arenes using Me3SiCF3 was achieved with a broad substrate scope.
- Weng, Zhiqiang,Lee, Richmond,Jia, Weiguo,Yuan, Yaofeng,Wang, Wenfeng,Feng, Xue,Huang, Kuo-Wei
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experimental part
p. 3229 - 3232
(2011/07/31)
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- A broadly applicable copper reagent for trifluoromethylations and perfluoroalkylations of aryl iodides and bromides
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(Chemical Presented) Well compatible: The trifluoromethylations and perfluoroalkylations of aryl iodides and some aryl bromides with trifluoromethyl and perfluoroalkylcopper(I) phenanthroline complexes occur with broad scope at 25-50 8C (see scheme). The trifluoromethyl complex is prepared from inexpensive reagents and can be used in situ or isolated. The reactions tolerate a range of substituents and also occur with heteroaromatic systems.
- Morimoto, Hiroyuki,Tsubogo, Tetsu,Litvinas, Nichole D.,Hartwig, John F.
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supporting information; experimental part
p. 3793 - 3798
(2011/05/15)
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- Copper-catalyzed trifluoromethylation of aryl iodides with potassium (trifluoromethyl)trimethoxyborate
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Potassium (trifluoromethyl)trimethoxyborate is introduced as a new source of CF3 nucleophiles in copper-catalyzed trifluoromethylation reactions. The crystalline salt is stable on storage, easy to handle, and can be obtained in near-quantitative yields simply by mixing B(OMe)3, CF3SiMe3, and KF. The trifluoromethylation reagent allows the conversion of various aryl iodides into the corresponding benzotrifluorides in high yields under mild, base-free conditions in the presence of catalytic quantities of a CuI/1,10-phenanthroline complex.
- Knauber, Thomas,Arikan, Fatih,Roeschenthaler, Gerd-Volker,Goossen, Lukas J.
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experimental part
p. 2689 - 2697
(2011/04/15)
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- A NOVEL AND CONVENIENT METHOD FOR TRIFLUOROMETHYLATION OF ORGANIC HALIDES USING CF3SiR'3/KF/Cu(I) SYSTEM
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Fluoride ion induced cross-coupling reaction of organic halides with trifluoromethyltrialkylsilanes takes place in the presence of Cu(I) salts under mild reaction conditions to give the corresponding trifluoromethylated products in high yields.
- Urata, Hisao,Fuchikami, Takamasa
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- TRIFLUORMETHYLIERUNGSREAKTIONEN VON Te(CF3)2 MIT HALOGENBENZOLEN UND METHYLBENZOLEN
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Substituent effects on yields and regioselectivity of photochemical and thermal trifluoromethylation reactions of Te(CF3)2 with halogen benzenes and methyl benzenes are investigated under comparable conditions.All reactions lead to trifluoromethylated products.The yields of the thermal are always higher than those of the corresponding photochemical reactions.The reactivity of the halobenzenes increases in the series C6H5-F a sidereaction, but H-substitution is the primary reaction pathway.During the reactions with iodobenzene tellurium containing compounds are also formed.The reactions with methyl benzenes show an increase in reactivity in the series hexamethylbenzene mesitylene toluene p-xylene.In all cases only ring substituted products are detected.Reactions with toluene and p-xylene yield tellurium containing compounds as well as addition products.The 19F-n.m.r spectra of the products are given.
- Naumann, Dieter,Kischkewitz, Jurgen
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p. 283 - 299
(2007/10/02)
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- Reactions of Perfluoroalkanesulfonyl Chlorides with Aromatic Compounds Catalyzed by a Ruthenium(II) Complex
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The reactions of perfluoroalkanesulfonyl chlorides with aromatic compounds in the presence of a catalytic amount of dichlorotris(triphenylphosphine)ruthenium(II) were found to give perfluoroalkylated compounds in good yield.
- Kamigata, Nobumasa,Fukushima, Takamasa,Yoshida, Masato
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p. 649 - 650
(2007/10/02)
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- Reactions of Trifluoromethyl Bromide and Related Halides: Part 10. Perfluoroalkylation of Aromatic Compounds induced by Sulphur Dioxide Radical Anion Precursors
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Perfluoroalkylation of electron-rich aromatic compounds with trifluoromethyl bromide, or long-chain perfluoroalkyl iodides, was performed in the presence of sodium dithionite or zinc-sulphur dioxide.This alkylation occurred at the ortho and para positions relative to the amino or hydroxy substitutent.Pyrroles were perfluoroalkylated regioselectively at the 2-position.This alkylation was interpreted as a radical aromatic substitution; the formation of the perfluoroalkyl radical can be induced by a single-electron transfer from sulphur dioxide radical anion to the perfluoroalkyl halide.
- Tordeux, Marc,Langlois, Bernard,Wakselman, Claude
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p. 2293 - 2299
(2007/10/02)
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- Trifluoromethyl substituted spirooxazine photochromic dyes
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The organic photochromic composition of this invention comprises trifluoromethyl substituted spiro (indoline-2,3'-(3H) napth-(2,1-b)(1,4)oxazine) (SO) dyes. This new class of (SO) photochromic compounds has a more neutral color when subjected to ultraviol
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- Process for the preparation of compounds containing a difluoromethylene or trifluoromethyl group
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A process for the preparation of compounds containing a difluoromethylene or trifluoromethyl group. A compound containing a carbonyl group, preferbly an acid, acid halide, amide, ketone or any compound containing a perhaloalkylcarbonyl moiety is placed, in anhydrous liquid hydrofluoric acid, in contact with boron trifluoride in a quantity such that the absolute pressure of boron trifluoride in the reaction system is at least one bar for a time sufficient to convert the carbonyl group to a difluormethylene or trifluoromethyl group. The compounds obtained are useful as synthesis intermediates in the pharmaceutical, plant-protection and dye industries, as anesthetics or as heat-transfer and lubricating fluids.
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- MECHANISMS OF FREE-RADICAL REACTIONS. XXII. KINETICS OF THE FREE-RADICAL HALOGENATION OF ORTHO-SUBSTITUTED TOLUENES
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The free-radical chlorination and bromination of ortho-substituted toluenes were studied by the method of competing reaction.It was shown that differences in the effect of the ortho and para substituents on the rate of the free-radical hydrogen abstraction stage are due mainly to the different degrees of development of the polar effect.The steric effects of the substituents have practically no effect on the reaction rates.
- Dneprovskii, A. S.,Labeish, V. V.
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p. 2013 - 2016
(2007/10/02)
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- A New Method for the Trifluoromethylation of Aromatics
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A new method is described for introducing a CF3-group, by a single-step synthesis, into aromatic compounds.This trifluoromethylation is done by means of a mixture consisting of HF/CCl4 and the aromatic compounds.The reaction is thought to be of a Friedel-Crafts type and limited to aromatics which are not substituted by electron withdrawing groups.
- Marhold, A.,Klauke, E.
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p. 281 - 292
(2007/10/02)
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